Double‐Network Confined Supramolecular Phosphorescence Light‐Harvesting Boosting Photocatalysis

Abstract

environment for luminophores, but also restricts the movement of guests, inhibits the nonradiative transition of the excited state of luminophores, reduces the collision of solvent molecules, giving a confined microenvironment for phosphorescence emission. [14][15][16] Tian et al. [17] reported that CB[8] could bind with triazine bridged bromophenyl pyridine derivative to form a stable 2:2 hostguest complex, then could be excited by visible light to give tunable phosphorescence emission in aqueous solution. We reported a red phosphorescence emission "supramolecular pins" with ultrahigh quantum yield up to 99.38% based on CB[8] and alkyl chain bridged phenyl pyridine salt. [18] Thus, the confinement of CBs can effectively induce RTP emission of organic luminophores. In addition, nanosized supramolecular assemblies not only have assemble confined effect is benefit to improving the luminescent properties of chromophores, but also could further load dyes as energy acceptors to form efficient energy transfer system. Therefore, taking advantage of the strategy of confinement of macrocyclic compounds and assemble could effectively promote the development of PLH systems.Artificial light-harvesting system with the characteristics of large donor-acceptor ratio and high energy transfer efficiency, which is convenient to realize large Stokes shift luminescence emission, showing fascinating application prospects in the fields of cell imaging, [19][20][21] sensor detection, [22] catalysis, [23][24][25] and luminescent materials. [26][27][28] George et al. reported that luminescent supramolecular hybrid could be facilely fabricated by the cationic dibromophthalimide derivative and inorganic clay via electrostatic interaction, exhibiting efficient phosphorescence emission with high quantum yield as 41.8%, which also could be doped with energy acceptor to form artificial lightharvesting system. [29] We reported that dibromophthalimide derivative could coassemble with CB[7] and amphipathic sulfonatocalix[4]arene to form multivalent phosphorescence assembly, then loading dyes as energy acceptors to construct near-infrared emission PLH system with cascaded energy transfer for cell imaging. [20] However, the application of pure organic PLH system with long lifetime luminescence in photocatalysis reaction has not been reported as best we know. Herein, a doublenetwork PLH system was successfully fabricated by in situ copolymerization of bicationic vinyl bromophenyl pyridine derivative (G), CB[8], acrylamide, and hyaluronic acid modified

Aromatic Bridged Bis(triphenylamine) Cascade Assembly Achieved Tunable Nanosupramolecular Morphology and NIR Targeted Cell Imaging

“…Figure b demonstrated that the fluorescence signal of G/CB[8] (PD) at 380 nm was not found, and the strong signal still existed (510 nm) in phosphorescence spectroscopy (delayed 50 μs), indicating that the peak at 510 nm should be the long lifetime species. After nitrogen was bubbled in PD solution, the phosphorescence intensity of PD was obviously enhanced (Figure S32a), and the lifetime was increased from 530.60 to 780.92 μs (Figures S32b and S33), indicating the long lifetime signal at 510 nm should be the phosphorescence peak. , The UV–vis spectroscopy experiments (Figure S34) showed that CB[8] could include G to form a stable 2:1 supramolecular complex ( K s = 1.06 × 10 11 M –2 ), and was propitious to the phosphorescence emission of PD. In addition, we also investigated the binding model between the G and CB[8] or α-cyclodextrin (α-CD) by NMR experiments.…”

Polymerization boosting cascade energy transfer based on opened glucopyranosyl β-cyclodextrin

“…These results jointly confirmed that the energy transfer from ACD/CS to the chromophore in this supramolecular polymer should be a Fo ¨rster mechanism. 21 Based on the above results, we proposed a possible energy transfer mechanism in this system. The energy transfer from the singlet state of ACD/CS (donor) to the acceptor, further turns to the ground state and generates the fluorescence of the acceptor (Fig.…”

Smart organic materials based on macrocycle hosts

“…Taking advantage of the rigid environment and the inhibition of the molecular motions offered by the polymer matrixes, RTP materials based on the crosslinking of supramolecular polymers have been achieved assisted by the host-guest interactions of CD and CB[n]. 34,35 In particular, a type of ''supramolecular pins'' with efficient phosphorescence in both solutions and solid phases was developed by Liu and coworkers following ''one host with one guest'' binding mode between CB [8] and phenylpyridinium salt, of which the afterglow was substantially promoted by further incorporation into polymer matrixes with high phosphorescence efficiency (Fig. 3b).…”